WO2013066906A1 - Non-halogen flame retardant polymers - Google Patents

Non-halogen flame retardant polymers Download PDF

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Publication number
WO2013066906A1
WO2013066906A1 PCT/US2012/062639 US2012062639W WO2013066906A1 WO 2013066906 A1 WO2013066906 A1 WO 2013066906A1 US 2012062639 W US2012062639 W US 2012062639W WO 2013066906 A1 WO2013066906 A1 WO 2013066906A1
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Prior art keywords
flame retardant
polymer
meth
monomer
composition
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PCT/US2012/062639
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English (en)
French (fr)
Inventor
John Ta-Yuan Lai
Ti Chou
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Lubrizol Advanced Materials, Inc.
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Priority to EP12783806.8A priority Critical patent/EP2773722B1/en
Priority to US14/354,723 priority patent/US9290639B2/en
Priority to MX2014005066A priority patent/MX351640B/es
Priority to CA2853948A priority patent/CA2853948C/en
Priority to JP2014539145A priority patent/JP6150812B2/ja
Priority to CN201280061151.7A priority patent/CN104011176B/zh
Priority to BR112014010342-9A priority patent/BR112014010342B1/pt
Priority to ES12783806.8T priority patent/ES2671925T3/es
Priority to KR1020147014714A priority patent/KR102064933B1/ko
Publication of WO2013066906A1 publication Critical patent/WO2013066906A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
    • C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
    • C07F9/3826—Acyclic unsaturated acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
    • C07F9/3834—Aromatic acids (P-C aromatic linkage)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/14—Macromolecular materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B01D39/20—Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
    • B01D39/2068—Other inorganic materials, e.g. ceramics
    • B01D39/2082—Other inorganic materials, e.g. ceramics the material being filamentary or fibrous
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints

Definitions

  • the disclosed technology relates to non-halogen flame retardant compositions comprising phosphorus in complex with nitrogen.
  • Halogens i.e., fluorine, chloride, bromine and iodine
  • halogens are very active chemical elements and can generate toxic substances, such as dioxin and difuran, upon degradation. These substances can accumulate in a human body for long periods of time and cause environmental hormone problems.
  • fluorine, chloride and bromine in particular, have been known to cause severe depletion of ozone. For this reason, the use of halogens, whether as flame retardants or in other applications, is increasingly regulated. Accordingly, there is a need for non-halogenated flame retardants.
  • One method of obtaining a flame retardant composition is to include phosphorus in the composition.
  • U.S. Patent No. 5,281 ,239 to Chatelin et al., issued January 25, 1994 teaches a method of grafting a fibrous material with phosphoric acid ethylenic esters of the general formula:
  • the graft rate of the ester is taught to be less than or equal to 20%.
  • JP2007182652A to Toshio published July 19, 2007, teaches flame retardant additives comprising a mixture of an organic phosphorus-base-flame- retarder and a nitrogen type flame retardant.
  • CN 102071032 teaches the use in combination of phosphorus containing and nitrogen containing flame retardants.
  • novel flame retardant monomer composition can comprise a) a group derived from one of a (meth)acrylic acid, (meth) aery 1 amide, or vinylbenzene, b) a polyphosphate moiety, and c) an amine species.
  • an ethylenically unsaturated monomer of (a) is covalently bonded directly or through a linking group to the polyphosphate moiety of b), forming a precursor monomer unit.
  • the amine species of c) is in complex with the covalently bonded polyphosphate moiety of b) in the precursor monomer unit.
  • the novel flame retardant monomer composition can be produced by reacting the precursor monomer unit with the amine species.
  • a flame retardant polymer in another aspect of the invention, there is provided a flame retardant polymer.
  • the flame retardant polymer can be a homopolymer of flame retardant monomeric units equivalent to, i.e., derived from, the novel flame retardant monomer composition, or a copolymer of monomeric units equivalent to the novel flame retardant monomer compositions having varying a), b) and c).
  • the flame retardant polymer can additionally comprise monomeric units equivalent to ethylenically unsaturated monomers that are not covalently bonded to a polyphosphate moiety.
  • At least 20% of the monomers in the polymer are monomeric units equivalent to the novel flame retardant monomer compositions of the simplest aspect of the invention, and from 0.1 % to about 80% of the monomers in the polymer can be monomeric units equivalent to the ethylenically unsaturated monomers that are not covalently bonded to a polyphosphate moiety.
  • Such a copolymer can be comprised of at least 1 wt.% P and have a number average molecular weight (Mn) of at least about 1000 g/mole.
  • At least 90% of the monomers in the flame retardant polymer can comprise a combination of monomeric units equivalent to the ethylenically unsaturated monomers that are not covalently bonded to a polyphosphate moiety and monomeric units equivalent to the novel flame retardant monomer compositions of the simplest aspect of the invention.
  • a flame retardant polymer can be produced by several routes.
  • the novel flame retardant monomer composition of the simplest aspect can be free-radically polymerized to form a flame retardant polymer.
  • the flame retardant polymer can be produced by free radically polymerizing the precursor monomer units and subsequently reacting the polymerized product with the amine species.
  • ethylenically unsaturated monomer units that are not covalently bonded to a polyphosphate moiety can be in included in the free radical polymerization.
  • flame retardant compositions are provided.
  • the flame retardant composition can comprise the flame retardant polymers along with other additives.
  • additives such as flame retardant additives and other polymers may be blended in the flame retardant compositions along with the flame retardant polymer.
  • wt.% means the number of parts by weight of ingredient per 100 parts by weight of the composition or material of which the ingredient forms a part.
  • a polyphosphate moiety refers specifically to a group containing a phosphorus atom bonded to three oxygen ions (phosphonate) or a phosphorus atom bonded to four oxygen ions (phosphate).
  • the polyphosphate moiety may contain mono-, di-, tri-, or higher phosphate, or a mono-, and/or di-phosphonate, and in particular a monophosphate, diphosphate, triphosphate or monophosphonate.
  • the polyphosphate moiety is a mono-, di-, or tri-phosphate.
  • hydrocarbyl substituent or “hydrocarbyl group” is used in its ordinary sense, which is well-known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character.
  • hydrocarbyl groups include:
  • hydrocarbon substituents that is, aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic-, aliphatic-, and alicyclic-substituted aromatic substituents, as well as cyclic substituents wherein the ring is completed through another portion of the molecule (e.g., two substituents together form a ring);
  • aliphatic e.g., alkyl or alkenyl
  • alicyclic e.g., cycloalkyl, cycloalkenyl
  • aromatic-, aliphatic-, and alicyclic-substituted aromatic substituents as well as cyclic substituents wherein the ring is completed through another portion of the molecule (e.g., two substituents together form a ring);
  • substituted hydrocarbon substituents that is, substituents containing non- hydrocarbon groups which, in the context of this invention, do not alter the predominantly hydrocarbon nature of the substituent (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulfoxy);
  • hetero substituents that is, substituents which, while having a predominantly hydrocarbon character, in the context of this invention, contain other than carbon in a ring or chain otherwise composed of carbon atoms.
  • Heteroatoms include sulfur, oxygen, nitrogen, and encompass substituents as pyridyl, furyl, thienyl and imidazolyl.
  • an alkyl group containing an oxygen atom is refered to as an alkoxyl group.
  • coating is used herein to refer to impregnation, saturation, roller, brush, spray, foam and curtain coating and similar procedures.
  • polymer refers to the product of a polymerization reaction in which the molecules of one or more monomers are linked together to form large molecules whose molecular weight is a multiple of that of the one or more monomers. These polymers may be homopolymers or copolymers. These polymers may be linear polymers, branched polymers, cross- linked polymers, or a mixture of two or more thereof.
  • homopolymer is used herein to refer to a polymer resulting from the polymerization of a single monomer.
  • copolymer is used herein to refer to a polymer resulting from the polymerization of two or more chemically distinct monomers.
  • linear polymer refers to a polymer in which the molecules form long chains without branches or cross-linked structures.
  • branched polymer refers to a polymer in which the molecules form a main chain or polymer backbone and one or more additional relatively short chains are attached to the main chain or polymer backbone.
  • cross-linked polymer refers to a polymer in which the polymer molecules are linked to each other at points in their structures other than at the ends of the polymer chains.
  • halogen-free or non-halogenated polymer refers to a polymer that does not have any halogen atoms attached to it.
  • the halogen-free polymer is a chlorine-free polymer.
  • halogen-free does not exclude halogen that may be present at contaminate levels, for example, levels of up to about 5% by weight, and in one embodiment up to about 2% by weight, and in one embodiment up to about 1% by weight, and in one embodiment up to about
  • 0.5% by weight and in one embodiment up to about 0.2% by weight, and in one embodiment up to about 0.1 % by weight.
  • the resultant monomeric unit within the polymer will have a structure that is slightly altered from the starting monomer.
  • the monomeric unit is equivalent to, i.e., derived or derivable from, the starting monomer, having the same atoms in the same relative positions to each other as in the monomer, only the carbon to carbon double bond of the monomer is converted to a carbon to carbon single bond in the monomeric unit and the excess electrons from that conversion of the monomer are used to bond each monomeric unit to adjacent carbon atoms on an adjacent repeating unit of the polymer.
  • reference herein to a polymer comprising a monomer means that the polymer is comprised of monomeric units equivalent to,
  • novel flame retardant monomer composition can comprise a) an ethylenically unsaturated monomer, such as, for example, a group derived from one of a (meth)acrylic acid, (meth) aery 1 amide, or vinylbenzene, b) a polyphosphate moiety, and c) an amine species.
  • an ethylenically unsaturated monomer such as, for example, a group derived from one of a (meth)acrylic acid, (meth) aery 1 amide, or vinylbenzene
  • b) a polyphosphate moiety such as, for example, a group derived from one of a (meth)acrylic acid, (meth) aery 1 amide, or vinylbenzene
  • b) a polyphosphate moiety such as, for example, a group derived from one of a (meth)acrylic acid, (meth) aery 1 amide, or vinylbenzene
  • vinylbenzene can be styrene or an alkyl substituted vinylbenzene, such as, for example, a-methyl styrene, l-methyl-2-vinylbenzene, l-methyl-3 -vinylbenzene, l -methyl-4- vinylbenzene and the like.
  • ethylenically unsaturated monomer there is also contemplated, for example, 2-hydroxyethyl (meth)acrylate (HEMA).
  • HEMA 2-hydroxyethyl (meth)acrylate
  • other monomers such as hydroxypropyl (meth)acrylate or 4-hydroxybutyl (meth)acrylate are contemplated.
  • 2-hydroxyethyl (meth)acrylamide, hydroxypropyl (meth) aery 1 amide, polyethyleneglycol (meth)acrylate and the like are contemplated.
  • one of the ethylenically unsaturated monomers of a) is covalently bonded directly or through a linking group to the polyphosphate moiety of b), forming a precursor monomer unit.
  • the amine species of c) is in complex, typically a salt, with the covalently bonded polyphosphate moiety of b) in the precursor monomer unit.
  • the ethylenically unsaturated monomers of a), the polyphosphate moiety of b) and the amine species of c) are disclosed separately, in the novel flame retardant monomer composition the amine species are present in complex with the polyphosphate moiety, and the polyphosphate moiety is covalently bonded to the ethylenically unsaturated monomers of a).
  • a flame retardant monomer is one that imparts flame retardancy to a polymer in which it is incorporated.
  • Example embodiments of the novel flame retardant monomer composition can be, for example, phosphate esters of 2-hydroxyethyl methacrylate complexed with guanyl urea and phosphonic esters of 2-hydroxylethyl methacrylate complexed with guanyl urea.
  • the novel flame retardant monomer composition may be represented, for example, by the novel flame retardant monomer composition of formula I.
  • the term "derived” can mean derived or derivable.
  • the phosphorus containing monomer can be derived or derivable from (meth)acrylic acid or (meth)acrylamide.
  • derivable it is meant that derivation of the monomer is possible from (meth)acrylic acid or (meth)acrylamide, but may also be derived from other materials, such as other (meth)acrylic acid sources, for example, (meth)acrylonitrile in a Ritter reaction.
  • the (meth)acrylic acid derived flame retardant monomer can be made using a (meth)acrylic acid ester.
  • the monomer product contains the (meth)acrylic acid or (meth) aery 1 amide moiety just the same as if it were derived from (meth)acrylic acid or (meth)acrylamide.
  • a precursor monomer unit can be formed from a polyphosphate moiety and an ethylenically unsaturated monomer of a).
  • X is O or NH
  • R 3 is a C0-C50 hydrocarbyl linking group having oxygen and/or nitrogen atoms substituted for up to 20 of the carbon atoms,
  • n can be between about 1 to about 10, or about 1 to about 8, or about 1 to about 6, and preferably from about 1 to about 3,
  • R 4 is H, M + , or alkyl
  • R 5 is H, or M + .
  • M + is a counterion selected from elements in Groups I and II of the periodic table, or ammonium.
  • ammonium means NH 4 , or mono-, di-, tri-, or tetra- alky 1 ammonium .
  • the polyphosphate moiety can contain a tribasic acid of phosphorus.
  • the polyphosphate moiety can be derived from carboxyethyl monophosphate, carboxyethyl monophosphonate, carboamidoethyl monophosphate, carboamidoethyl monophosphonate, phenethyl monophosphate, or phenethyl monophosphonate.
  • the precursor monomer unit i.e., the unit comprised of the (meth)acrylic acid, (meth)acrylamide, or vinylbenzene covalently bonded to a polyphosphate moiety
  • the precursor monomer unit may be purchased commercially, but non- commercial precursor monomer units are also contemplated herein.
  • commercial precursor monomer units are mixtures, such as, for example, SipomerTM Pam-4000 available from Rhodia, which is a major part 2 -hydroxy ethyl (meth)acrylate monophosphate ester (HEMA) and a minor part bis(2-hydroxyethyl (meth)acrylate) phosphate ester.
  • HEMA 2 -hydroxy ethyl (meth)acrylate monophosphate ester
  • Such mixtures are contemplated herein, as well as precursor monomer units that are pure compositions.
  • HEM A polyphosphate can also be made directly from HEM A and phosphorus pentoxide or phosphoric acid.
  • other monomers such as hydroxypropyl (meth)acrylate or 4-hydroxybutyl (meth)acrylate could be used in place of HEMA.
  • precursor monomer units can include, polyethylene glycol (meth)acrylate phosphate ester (available as PAM-100 from Rhodia), polypropylene glycol (meth)acrylate phosphate ester (available as PAM- 200 from Rhodia), methacrylamidoethyl phosphonic acid, vinylbenzene phosphonic acid, vinyl phosphonic acid, and isopropenyl phosphonic acid.
  • the amine species c) can have a molecular weight of from about 17 to about 3000 g/mole.
  • Suitable amine species for the novel flame retardant monomer composition can be derived from, for example, dicyandiamide, alkylamines, such as, for example, trimethylamine, triethylamine, triethanolamine, and dimethylamine, or guanidine.
  • Suitable amine compounds are urea, substituted akyl ureas, thiourea, akyl thiourea, cyanamide, ethylenediurea, aniline, ethyleneamines, guanidine, guanamine, benzoguanamine, acetoguanamine, glycoluril, acrylamide, methacrylamide, melamine, benzene sulfonamide, naphthalene sulfonamide, toluene sulfonamide, ammeline, ammelide, guanazole, phenylguanazole, carbamoylguanazole, dihydroxyethyleneurea, ethyleneurea, propylene urea, melem (C6H 6 Nio), melam (CeHgNn), octadecylamide, glycine, and their mixtures.
  • a specific example of a suitable amine species for use in the novel flame retardant monomer composition can be guany
  • the flame retardant polymers may be homopolymers or copolymers comprising the novel flame retardant monomer compositions of the simplest aspect of the invention.
  • the flame retardant polymers may be a copolymer of A) at least one ethylenically unsaturated monomer unit that is not covalently bonded to a polyphosphate moiety, and B) the novel flame retardant monomer compositions of the simplest aspect of the invention.
  • the polymer can contain one or more of the same or different ethylenically unsaturated monomer units of A) and/or one or more of the same or different novel flame retardant monomer compositions of B).
  • the ethylenically unsaturated monomer units of A) can be from 0% or 0.1 % of the monomers in the polymer to about 80% of the monomers in the polymer. Likewise, up to about 65% of the monomers in the flame retardant polymer may be ethylenically unsaturated monomer units of A). Alternately, up to about 70% or 75% of the monomers may be the ethylenically unsaturated monomer units of A).
  • the ethylenically unsaturated monomer units of A) of the present invention can serve, among other things, to provide particular physical characteristics to the polymer.
  • one of ordinary skill in the art may choose the appropriate ethylenically unsaturated monomer for the flame retardant polymer based on the particular physical characteristics desired for a particular application of the flame retardant polymer.
  • ethylenically unsaturated monomers not covalently bonded to a polyphosphate moiety suitable for use in the flame retardant polymer can be, for example, one or more of, styrene, C 1 -C40 alkyl (meth)acrylates, C 1 -C40 (meth)acrylamides, acrylamide, N-methylolacrylamide, acrylonitrile, acrylic acid, methacrylic acid, itaconic acid, maleic acid, 2-acrylamido-2-methylpropane sulfonic acid, C 1 -C40 hydroxyalkyl (meth)acrylates, (acetoacetoxy)ethyl methacrylate, C 1 -C40 hydroxyalkyl (meth)acryl amide, diacetone acrylamide, vinyl esters, butadiene, isoprene and dimeric or multi- derivative compounds thereof.
  • the flame retardant polymer can be non-halogenated, halogenated ethylenically unsaturated monomers, such as, for example, vinyl chloride, are also contemplated herein as suitable ethylenically unsaturated monomer units of A) in the flame retardant polymers.
  • the flame retardant polymer according to the invention at least 20% of the monomers in the polymer are selected from the novel flame retardant monomer composition. It is also contemplated that up to 100% of the monomers making up the flame retardant polymer can be the novel flame retardant monomer composition. It is also contemplated that at least 30%, at least 40%, or at least 50% of the monomers in the flame retardant polymer can be the novel flame retardant monomer composition. In certain flame retardant polymers according to the invention, at least 35%, at least 45%, and at least 55% of the monomers may be the novel flame retardant monomer composition.
  • At least 80%>, or at least 85%, or at least 90%, and in some embodiments at least 95% of the monomers in the polymer comprise a combination of the ethylenically unsaturated monomers that are not covalently bonded to a polyphosphate moiety and the novel flame retardant monomer compositions.
  • the flame retardant polymer is comprised of at least 1 wt.% phosphorus and has a number average molecular weight (Mn) of at least about 1000 g/mole.
  • the flame retardant polymer may contain phosphorus at from about 1 wt.% to about 15 wt.%, or from about 2 wt.% to about 14 wt.%, or from about 5 wt.% to about 10 wt.%.
  • the flame retardant polymer contains at least 7 wt.% phosphorus and in another the flame retardant polymer contains about, 9 wt.% phosphorus and in another 10.6 wt.% phosphorus.
  • the Mn of the flame retardant polymer should be at least 1000 g/mole.
  • the Mn can also be from about 50,000 g/mole to about 1 ,000,000 g/mole, or from about 100,000 g/mole to about 750,000 g/mole.
  • the Mn of the flame retardant polymer can be about 200,000 g/mole to about 500,000 g/mole.
  • the flame retardant polymers comprised of novel flame retardant monomer compositions provide better flame retardant performance than similar polymers that do not include a polyphosphate/amine species as does the novel flame retardant monomer composition.
  • the flame retardant polymer may be produced by first producing a mixture of at least one novel flame retardant monomer composition, and subsequently free-radically polymerizing the mixture to form a flame retardant polymer, for example, as shown in formula II.
  • ethylenically unsaturated monomer units of A) can be added to the polymerization mixture of the at least one novel flame retardant monomer composition so that the polymerization results in a flame retardant polymer in which 0% to about 80% (or about 0.1 to 75%, or 1 to 65% or 5 to 55%) of the monomers are ethylenically unsaturated monomer units of A) and at least 20% of the monomers are the at least one novel flame retardant monomer composition.
  • a flame retardant polymer can be produced wherein up to 80%>, or up to 85%>, or up to 90%> of the monomer units in the polymer can be the novel flame retardant monomer composition.
  • up to 95% or up to 100% of the monomer units in the polymer can be the novel flame retardant monomer composition.
  • the mixture of the at least one novel flame retardant monomer composition can be produced, in one embodiment, by reacting a mixture of at least one precursor monomer unit with a mixture of at least one amine species for between 10 minutes and 8 hours, preferably about 1 and 5 hours, at a temperature of between about 20°C and 100°C, preferably 70°C to 95 °C, to form the mixture of the at least one novel flame retardant monomer composition.
  • the flame retardant polymer may be produced by first producing a pre-cursor polymer by free-radically polymerizing precursor monomer units along with enough ethylenically unsaturated monomer units of A) to produce a polymer in which 0% to about 80% of the monomers are ethylenically unsaturated monomer units of A) and at least 20% of the monomers are precursor monomer units. Subsequent to polymerization, the precursor polymer may be reacted with enough amine species to complex the polyphosphate moieties in the precursor monomer units, as shown, for example, in formula III.
  • a flame retardant polymer can be produced wherein up to 30%, or up to 35%, or up to 40% of the monomer units in the polymer can be covalently bonded with polyphosphate moieties.
  • a counterion may be introduced into the compound during pH adjustment.
  • NaOH, KOH, ammonium hydroxide or alkyl ammonium hydroxide may be employed for pH adjustment, resulting in substitution of the hydrogen of one or both of the hydroxyls with a counterion, such as Na + , K + , ammonium, or alkyl ammonium.
  • a polymerization catalyst or other standard catalyst may be employed to assist polymerization.
  • polymerization catalysts can be alkali metal hypophosphite salts, such as sodium hypophosphite, alkali metal phosphites, alkali metal polyphosphates, alkali metal dihydrogen phosphates, polyphosphoric acids, and alkyl phosphinic acids.
  • alkali metal hypophosphite salts such as sodium hypophosphite, alkali metal phosphites, alkali metal polyphosphates, alkali metal dihydrogen phosphates, polyphosphoric acids, and alkyl phosphinic acids.
  • use of a polymerization catalyst can result in up to 95%, or up to 97.5%, or even up to 100% of the monomer units in the polymer covalently bonded with polyphosphate moieties.
  • a polymerization catalyst can result in up to 80%>, or up to 85%, or up to 88%, or even up to 90% of the monomer units in the polymer covalently bonded with polyphosphate moieties.
  • Solvent can be employed at any point in the processes, including during addition and reaction of the vinyl monomers used in the polymerization.
  • the mixture of the at least one precursor monomer unit can be obtained commercially, or by readily known processes to those of ordinary skill in the art.
  • the at least one precursor monomer unit can be made directly from the reaction of an alkoxyl (meth)acrylate with phosphorus pentoxide in water.
  • the polyphosphate to amine species (P:N) ratio in the amine species reaction step can be from about 1 :0.2 to about 1 : 15.
  • the P:N ratio can also be from about 1 :0.5 to about 1 : 10, or from about 1 : 1 to about 1 :5.
  • the amine species reaction step may be performed in the presence of water.
  • the reaction step may be completed by reacting the precursor monomer units or precursor polymer with dicyandiamide and water.
  • the reaction with dicyandiamide and water will result in the production of a guanyl urea, which guanyl urea can then complex with the polyphosphate moiety in the precursor monomer units.
  • the complexation reaction may result in other by-products, which by-products are contemplated herein.
  • free radical polymerization or copolymerization of the monomers may be by any polymerization process, such as, for example, by dispersion polymerization, solution polymerization, photo-polymerization, or radiation polymerization.
  • Emulsion polymerization may be used.
  • the monomers may be emulsified with an anionic, cationic, or nonionic surfactant or dispersing agent, or compatible mixtures thereof such as a mixture of an anionic and a nonionic surfactant, using, for example, from about 0.05% to about 5% by weight of a surfactant or dispersing agent based on the weight of the monomer.
  • Suitable cationic dispersion agents include lauryl pyridinium chloride, cetyldimethyl amine acetate, and alkyldimethylbenzylammonium chloride, in which the alkyl group has from 8 to 18 carbon atoms.
  • Suitable anionic dispersing agents include, for example, alkali fatty alcohol sulfates, such as sodium lauryl sulfate, and the like; arylalkyl sulfonates, such as potassium isopropylbenzene sulfonate, and the like; alkali alkyl sulfosuccinates, such as sodium octyl sulfosuccinate, and the like; and alkali arylalkylpolyethoxyethanol sulfates or sulfonates, such as sodium t- octylphenoxypolyethoxyethyl sulfate, having 1 to 5 oxyethylene units, and the like.
  • Suitable non-ionic dispersing agents include, for example, alkyl phenoxypolyethoxy ethanols having alkyl groups of from about 7 to 18 carbon atoms and from about 6 to about 60 oxyethylene units such as, for example, heptyl phenoxypolyethoxyethanols; ethylene oxide derivatives of long chained carboxylic acids such as lauric acid, myristic acid, palmitic acid, oleic acid, and the like, or mixtures of acids such as those found in tall oil containing from 6 to 60 oxyethylene units; ethylene oxide condensates of long chained alcohols such as octyl, decyl, lauryl, or cetyl alcohols containing from 6 to 60 oxyethylene units; ethylene oxide condensates of long-chain or branched chain amines such as dodecyl amine, hexadecyl amine, and octadecyl amine, containing from 6 to 60 oxyethylene units;
  • High molecular weight polymers such as hydroxyethyl cellulose, methyl cellulose, polyacrylic acid, polyvinyl alcohol, and the like, may be used as emulsion stabilizers and protective colloids.
  • the monomers can be polymerized without a surfactant.
  • the polymerization may be initiated in the presence of a small particle size preformed emulsion polymer (e.g., seed polymerization), or unseeded. Seeded polymerization may yield an aqueous dispersion of latex polymer having more uniform particle size than unseeded polymerization.
  • seed polymerization e.g., seed polymerization
  • Chain transfer agents may be used to control molecular weight and include mercaptans, polymercaptans, alcohols, and halogen compounds used in the polymerization mixture in order to moderate the molecular weight of the polymeric binder. Generally, from 0% to about 3% by weight, based on the weight of the polymeric binder, of C4-C 20 alkyl mercaptans, mercaptopropionic acid, or esters of mercaptopropionic acid, may be used.
  • the polymerization process may comprise a batch process, continuous process, staged process, or a process involving any other method. Each stage of a staged process may incorporate thermal or redox initiation of polymerization.
  • a monomer emulsion containing all or some portion of the monomers to be polymerized in a given stage may be prepared using the monomers, water, and emulsifiers.
  • a solution of initiator in water may be separately prepared.
  • the monomer emulsion and initiator solution may be co-fed into the polymerization vessel over the course of the emulsion polymerization of any stage of the process.
  • the reaction vessel itself may also initially contain seed emulsion and further may additionally contain an initial charge of polymerization initiator.
  • the temperature of the contents of the reaction vessel may be controlled by cooling to remove heat generated by the polymerization reaction or by heating the reaction vessel.
  • Several monomer emulsions may be simultaneously co-fed into the reaction vessel. When multiple monomer emulsions are co-fed, they may be of different novel flame retardant monomer composition. The sequence and rates at which the monomer emulsions are co-fed may be altered during the emulsion polymerization process.
  • the polymerization reaction mixture may be held at some temperature for a time and/or treated with a polymerization inhibitor prior to polymerization of the subsequent monomer emulsion(s).
  • the polymerization reaction mixture may be held at some temperature for a time and/or treated with a polymerization inhibitor before cooling to ambient temperature.
  • the pH of the polymers can be adjusted to about 3.0 to about 10.0 in the premix or in the emulsion polymer with commonly used base, such as, for example, ammonium hydroxide, sodium or potassium hydroxide, magnesium hydroxide, tri(m)ethyl amine and the like.
  • commonly used base such as, for example, ammonium hydroxide, sodium or potassium hydroxide, magnesium hydroxide, tri(m)ethyl amine and the like.
  • the flame retardant polymers may contain conventional ingredients such as solvents, plasticizers, pigments, dyes, fillers, emulsifiers, surfactants, thickeners, rheology modifiers, heat and radiation stabilization additives, defoamers, leveling agents, anti-cratering agents, fillers, sedimentation inhibitors, U.V. absorbers, antioxidants, flame retardants, etc. It may contain other polymeric species such as additional polymers in the forms of blends, interpenetrating networks, etc.
  • the flame retardant polymers may be blended with additional flame retardant additives, which are well known in the literature and art.
  • exemplary flame retardant additives include non-halogen flame retardants, such as melamine and melamine derivatives, such as melamine cyanurate, melamine borate, melamine phosphate, melamine molybdate; borates; organic phosphates, organic phosphinates such as, for example, ExolitTM OP 1230 and 131 1 available from Clariant, and phosphorus containing compounds, such as, 9, 10-dihydro-9-oxa-10- phosphaphenanthrene-10-oxide, tetrakis(hydroxymethyl)phosphonium chloride and bis [tetrakis(hydroxymethyl)phosphonium] sulfate; inorganic compounds such as aluminum trihydrate, antimony oxide, ammonium phosphate, ammonium polyphosphate, calcium carbonate, clay, and talc.
  • non-halogen flame retardants such as mel
  • the flame retardant polymers are desired to be non-halogenated, blending the flame retardant polymers with halogenated flame retardants, such as chlorinated and brominated compounds, such as pentabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, and hexabromocyclododecane, is contemplated herein. Often more than one flame retardant is used and frequently 3 or more flame retardants are combined in flame retardant formulations.
  • the level of flame retardants used in conjunction with the flame retardant polymers and copolymers of the present invention can be from about 1 to about 50 parts by weight of flame retardant additive per 100 parts by weight of the flame retardant polymer.
  • ethylenically unsaturated monomers can be chosen to impart particular physical properties to the flame retardant polymer
  • additional polymers can be blended with the flame retardant polymers and copolymers of the present invention to produce blends of further flame retardancy or with certain physical properties.
  • other polymers that may be blended can include polyurethane polymers, polyamide polymers, polyurea polymers, polyester polymers, polyacrylate polymers, phenolic resins or mixtures thereof.
  • the polymer may be combined with other commercial polymers or polymer dispersions by methods known to those skilled in the art.
  • the polymer may be used for forming hybrids with other polymers such as urethanes or silicones. This may be done by polymerizing additional monomers by emulsion or suspension polymerization in the presence of the polymer, blending the polymer with other preformed polymers, or synthesizing the polymer in the presence of other polymers.
  • the polymer may be mixed with a phenolic resin in a condensation reaction, preferably containing 0.5-10 wt% of N-methylol (meth)acrylamide .
  • Adjuvants useful in the preparation of the polymer and/or in its subsequent use may be added during or subsequent to the polymerization reaction. These may include auxiliary surfactants; defoamers such as, for example, SURFYNOLTM 104E and NopcoTM NXZ used at a level from about 0.001 to about 0.1 wt.% based on the weight of the monomer mixture; leveling agents such as, for example, SagTM Silicone Antifoam 47, used at a level from about 0.001 to about 0.1 wt.% based on the weight of the monomer mixture; antioxidants such as, for example, MAROXOLTM 20 and IRGANOXTM 1010 used at a level from about 0.1 to about 5 wt.% based on the weight of the monomer mixture; plasticizers such as, for example, FLEXOLTM plasticizer; and preservatives such as, for example, KATHONTM at a level of about 30 to about 45 parts per million (ppm), or
  • a premix mixture of 130g water, 6g Dextrol OC-40, 0.8g concentrated ammonium hydroxide, 6g of 48% N-methylol acrylamide (NMA), 89g ethyl acrylate (EA), 40g butyl methacrylate (BMA) and 67g SipomerTM PAM-4000 is prepared and added to the reactor. 6g water is used to flush the line after the addition. 30 minutes later, lg APS in 12g water is added in one portion and is allowed to react for 30 minutes before cooling to 62°C.
  • the product is mixed with 3g of 48% NMA, 34.3g EA and lg OC-40.
  • 220g water, 20g dicyandiamide, 0.5g of 30%> SLS and 0.03g OC-40 are mixed and stirred under nitrogen, then heated to 75 °C.
  • 0.55g SPS in 6g water is added in one portion, followed by the aforementioned premix in 3 hours.
  • 3g water is used to flush the line.
  • O. lg APS in 3g water is added and the reaction proceeds for 30 more minutes at 75 °C before cooling to 62°C.
  • the reaction mixture is then subject to a redox reaction twice, the same way as in the previous example. After cooling to less than 30°C, the product is filtered, and then blended with 45 g melamine cyanurate.
  • 292.5g SipomerTM PAM-4000 is mixed with 409.5g water, 1 17g dicyandiamide and 0.24g BHT, and brought to 90°C under air.
  • the reaction is heated at about 90 to about 92 °C for 5.5 hours and then cooled down.
  • the pH of the resultant solution is measured at 4.52.
  • a reactor containing 470g water and 15g sodium hypophosphite is heated to 75°C under a nitrogen atmosphere and 1.4g APS in 18g water is added. Thereafter the previously prepared solution is metered over three hours into the reactor with 15g of 48% N-methylol acrylamide.
  • the reaction temperature is brought up to 78°C. lOg of water is used to rinse the line.
  • the polymer of Sample 4 is used as a flame retardant additive with a resole phenolic resin.
  • the blend ratio is 50% phenolic resin/50% Sample 4, on a dry weight basis.
  • the polymer of Sample 4 is used as a flame retardant additive in a waterborne polyurethane dispersion.
  • the blend ratio is 50% polyurethane (Sancure® 2715 from Lubrizol Corporation)/50%> Sample 4, on a dry weight basis.
  • the polymer of Sample 4 is used as a flame retardant additive with a urea formaldehyde resin.
  • the blend ratio is 50% urea formaldehyde (From Arclin)/50% Sample 4, on a dry weight basis.
  • Paper impregnated with the compositions of Samples 1 , 2, 3, 5 and 6 are tested for flame retardancy against paper impregnated with several different controls.
  • the first control composition is HycarTM 26846, which is a commercial latex composition available from Lubrizol. It is tested on its own and with commercial flame retardant additives in a vertical burn test according to TAPPI 461 , Apparatus 3.1 to 3.4, both before water soaking and after being soaked in demineralized water for 24 hours and dried.
  • PAM-4000 is also tested on its own as a cast film dried at ambient temperature and cured at 300°F for 5 minutes.
  • PyrosanTM SYN is an organic phosphate compound available from Emerald Performance Materials.
  • AntiblazeTM LR3, LR4, and MC are ammonium polyphosphates available from Albemarle Corp.
  • MartinalTM OL-104 LE is an aluminum hydroxide available from Albemarle Corp.
  • MelapurTM MP is a melamine phosphate available from DSM Melapur.
  • Paper is impregnated with the flame retardant blend of Sample 7 or a resole type control polymer and tested for flame retardancy.
  • the sample and control are tested on their own in a vertical burn test according to TAPPI 461 , Apparatus 3.1 to 3.4, both before water soaking and after being soaked in demineralized water. Water soaking occurs by soaking the paper sample in demineralized for 2 hours, followed by drying. This process is repeated a total of 3 times for a total of 6 hours soaking before vertical burn testing.
  • Paper impregnated with the composition of Sample 8 is tested for flame retardancy against paper impregnated with SancureTM 2715, an aliphatic waterborne polyurethane type polymer.
  • the sample and control are tested on their own in a vertical burn test according to TAPPI 461 , Apparatus 3.1 to 3.4, both before water soaking and after being soaked in demineralized water. Water soaking occurs by soaking the paper sample in demineralized for 2 hours, followed by drying. This process is repeated a total of 3 times for a total of 6 hours soaking before vertical burn testing.
  • Paper impregnated with the composition of Sample 9 is tested for flame retardancy against paper impregnated with a urea formaldehyde resin from ArclinTM.
  • the sample and control are tested on their own in a vertical burn test according to TAPPI 461 , Apparatus 3.1 to 3.4, both before water soaking and after being soaked in demineralized water. Water soaking occurs by soaking the paper sample in demineralized for 2 hours, followed by drying. This process is repeated a total of 3 times for a total of 6 hours soaking before vertical burn testing.

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MX2014005066A MX351640B (es) 2011-10-31 2012-10-31 Polimeros retardantes de llama sin halogeno.
CA2853948A CA2853948C (en) 2011-10-31 2012-10-31 Non-halogen flame retardant polymers
JP2014539145A JP6150812B2 (ja) 2011-10-31 2012-10-31 非ハロゲン難燃性ポリマー
CN201280061151.7A CN104011176B (zh) 2011-10-31 2012-10-31 非卤素阻燃剂聚合物
BR112014010342-9A BR112014010342B1 (pt) 2011-10-31 2012-10-31 Composição, polímero retardante de chama, e, processos para produzir uma composição monomérica retardante de chama e um polímero retardante de chama
ES12783806.8T ES2671925T3 (es) 2011-10-31 2012-10-31 Polímeros retardantes de la llama no halógenos
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WO2014193754A1 (en) * 2013-05-28 2014-12-04 Lubrizol Advanced Materials, Inc. Non-halogen flame retardant polymers
CN104194152A (zh) * 2014-08-27 2014-12-10 江门市道生工程塑料有限公司 一种无卤阻燃聚丙烯复合材料及其制备方法
WO2016109262A1 (en) * 2014-12-30 2016-07-07 3M Innovative Properties Company Halogen-free flame retardant pressure sensitive adhesive and tape
WO2016109261A1 (en) * 2014-12-30 2016-07-07 3M Innovative Properties Company Halogen-free flame retardant pressure sensitive adhesive and tape
CN110183485A (zh) * 2019-06-03 2019-08-30 陕西科技大学 一种含磷量高的反应型磷酸酯类单体及其制备方法

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WO2014193754A1 (en) * 2013-05-28 2014-12-04 Lubrizol Advanced Materials, Inc. Non-halogen flame retardant polymers
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CN104194152A (zh) * 2014-08-27 2014-12-10 江门市道生工程塑料有限公司 一种无卤阻燃聚丙烯复合材料及其制备方法
WO2016109262A1 (en) * 2014-12-30 2016-07-07 3M Innovative Properties Company Halogen-free flame retardant pressure sensitive adhesive and tape
WO2016109261A1 (en) * 2014-12-30 2016-07-07 3M Innovative Properties Company Halogen-free flame retardant pressure sensitive adhesive and tape
US10526515B2 (en) 2014-12-30 2020-01-07 3M Innovative Properties Company Halogen-free flame retardant pressure sensitive adhesive and tape
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CN110183485A (zh) * 2019-06-03 2019-08-30 陕西科技大学 一种含磷量高的反应型磷酸酯类单体及其制备方法

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